Halogenated tris-phenols



hexyl, .cyclohexyl, methyl-cyclohexyl,

ited States Patent EMLQGENATEDTRIS-PHENOLS David 3. Beaver, Richmond Heights, Roland S. Shumard,

9 Claims. (Cl. 260-619) This invention relates to new and useful compositions of matter.

In accordance with this invention it has been found that halogenated tris-phenols of the general formula on OH on a, font- CHF- R2 X m x where R1 and R2 are like or .unlike hydrocarbon radicals, such .as methyL-ethyI, propyl, isopropyl, allyl, butyl, sec. buty l, amyl, Eisoamyl, .sec.- amyl hexyl, ,heptyl, Z-ethyl henzyl, phenethyl, pheinyl, .tolyl, :ethyl phenyl, and the like, where R3 :and R4 are like or unlike substituents selected from the grou p consisting .ofhydrogen atoms and short chain alkyl radicals, where X, X andX" are like or unlike halogenatoms and where and n are like or unlike whole numbers from ,1-3, and their corresponding alkali metal salts comprise a familyof highly useful compounds.

'The new compounds have .been found to have exceptional antisepticproperties in cosmetic formulations and in particular it has hen found that the new compounds when admixed with detergents in minor proportions form detergent compositions exhibiting antiseptic properties.

I The halogenated tris-phenols of this invention and their corresponding alkali metal salts are readily incorporated in a detergent'whether the latter be liquid or solid. The halogenated tris-phenols of this invention and their alkali metal salts remain permanently in the detergent composition and they neither afiect the lathe-ring, cleansing or physical properties of the detergent nor .do they impart an unpleasant odor nor discolor the finisihed detergent composition. The new compounds or" this invention when compounded with a detergentprodnce .a non-skin irritating detergent composition.

In its preferred embodiment the iuventionrelates to halogenated tris-phenols of the general formula V on on on R1O OH2-OCH20R2 XI V 11 and their corresponding alkali metal salts where R and As exemplary of the preferred halogenated tris-phenols of this invention are:

s 4 chloro a,a' (5,6 dichloro 3 4-chlo1'o-a,a-bis (S-chloro-Z-hydroxy-m-tolyl) -2,6-xylenol 4-chloro-a,a-bis (5-bromo-2-hydroxy-m-tolyl) -2, 6-xy1enol 4-bromo-a,a-bis (5-bromo-2-hydroxy-m-tolyl -2, 6-xylenol 4-chloro-a,a'-bis(5 chloro 3 ethyl-2-hydroxy-phenyl)- 2,6-xy1enol 4-chloro-a,a'-bis( 5 chloro-3-n-propyl-2 hydroxy-phenyl) 2,6-xylenol 4-chloro-a,a'-bis (3 n-but-yl-5-chloro-2-hydroxy-phenyl) 2,6-xylenol 4-chloro-a,a'-bis( 3 isobutyl-S-chloro-2 hydroxyphenyl)- 2,6-xylenol and their corresponding alkali metal salts. Of this preferred group the most effective antiseptic agents are the 4-halo-a,a-bis(5-halo 2 hydroxym-tolyl)-2,-6-xylenols and their corresponding alkali metal derivatives.

As exemplary of other tris-phenols of this invention which when admixed with a detergent form an eflicient antiseptic detergent composition are: 4-chloro-a,a -bis(5,6-dicliloro 2 hydroxy-m-tolyl) 2,6-

xylenol 4-bromo-a,a-bis(5,6-dichloro 2 hydroxy-m-tolyl) 2,6-

xylenol 4chloro-a,a'-bis(4,5,6-triclrloro 2 hydroxy-m-tolyl)-2,6-

xylenol 4-bromo-a,a-bis (4,5,6-trichloro-Z-hydroXy-m-tolyl) 2,6 xylenol 4 chloro a,a bis(5 bromo 6 chloro 2 hydroxym-tolyl);2,6-xylenol ethyl 2 hydrcrryphenyl) 2,6 xylenol 4 'bromo .a,-a' bis( 5,6 dibromo 3 hydroxy-phenyl) 2,6 xylenol 4 chloro a a bis(5,6 dichloro 2 tolylt) -3-methyl-2,6-xylenol 4 chloro ;a,a' bis(5,6 dichloro tolyl) -3-n butyl-2,6-xylenol 4 chloro a,a" bis( 5,6 diohloro tolyl) -3,5--.dimethy1-2,-6xylenol 4 chloro a,a' bis(5,6 .dichloro .3 droxy-phenyl)+3,5-dimethyl-2,6-xylenol 4 brcmo a,a bis (3 benzyl 5 chloro 2 hydroxyphenyl)-2,6-xylenol 4 chloro a,a bis(5 chloro droxy-phenyi)-2,6-xylenol 4 chloro a,a' bis(5 chloro 3 phenyI)-2,6-xylenol The corresponding alkali metal salts of these halogenated phenols when incorporated in detergents also produce satisfactory antiseptic detergent compositions.

As exemplary of the preparation of the new compounds of this invention the renewin i s illustrative:

EXAMPLE 1 Approximately 9.5 parts by weight of S-chloro-Z-hydroxy-'m-xylene-a;a'-diol and approximately 28.5 parts by Weight of 4-chloroo-cresol are intimately mixed with approximately 2:2 parts bfyweijg'ht of conc. hydrochloric acid in a suitable reaction vessel and heated at C. for approximately 15 minutes. The resultant semi-viscous mix is then slurried with approximately 35 parts by weigh: of a petroleum hydrocarbon (sp. gr. 0.7) consisting chief-r 1y of heptanes, allowed to stand; :Ihfi SOlldS subsequently filtered ofi and dried. A yield of approximately 62.4%

- r1 buty' 2- hydroxy m- 2 hydroxy m- 2 hydroxy mhydroxy m toiyD- -ethyl 2 hy- 3 cyclohexyl 2 hy- -phenyl 2 hydroxy- 0 by weight is obtained. The recrystallized product is a contain 24.1% chlorine and is believed to be 4-chloroa,a'-bis 5-chloro-2-hydroxy-m-tolyl) -2,6-xylenol,

Approximately 10.1 parts by weight of 5chloro-2-hydroxy-4-methyl-m-xylene-a,a-diol and approximately 28.5 parts by weight of 4-chloroo-cresol are intimately mixed with approximately 2.2 parts by weight of conoc. hydrochloric acid in a suitable reaction vessel and heated at 90 C. for approximately 15 minutes. The resultant semiviscous mix is then slurried with approximately 35 parts by Weight of a petroleum hydrocarbon (sp. gr. 0.7) consisting chiefly of heptanes, allowed to stand, the solids subsequently filtered oil and dried. A yield of approximately 65.1% by weight is obtained. The recrystallized product is a white needle-like solid possessing a melting point of 166-l67 C. Upon analysis the product is found to contain 23.8% chlorine and is believed to be 4-ch1oroa a'-bis 5 -chloro-2-hydroxy-m-tolyl) -3 -methyl-2,6-xylenol,

on OH on Ha C H2-- 0 Hr- C H:

C Ha

Cl 1 c1 EXAMPLE Ill Approximately 9.4 parts by weight of -chloro-2-hydroxy-m-xylene-a,a'diol and approximately 30.0 parts by weight of Z-ethyl-p-chlorophenol are intimately mixed with approximately 3.3 parts by weight of cone. hydrochloric acid in a suitable reaction vessel and heated at 90 C. for approximately 30 minutes. The resultant semiviscous mix is then slurried with approximately 22 parts by weight of toluene, allowed to stand, and the solids subsequently filtered off and dried. Upon recrystallization a 34.6% yield of a white crystalline material possessing a melting point of about 222-223" C. believed to be 4-chloro-a,a-bis(S-chloro 3 ethyl-Z-hydroxy-phenyD- 2,6-xylenol,

OH OH OH CH5 CH: CH (32H;

01 0] Cl is obtained.

EXAMPLE IV Approximately 9.4 parts by weight of 5-chloro-2-hydroxy-m-xylene-a,a' diol, approximately 30.0 parts by weight of 2-benzyl-p-chlorophenol, approximately 25 parts by weight of glacial acetic acid, and approximately 9 parts by weight of cone. sulfuric acid are intimately mixed in a suitable reaction vessel and heated on a steam bath for three hours. Upon steam distilling the reaction mix the viscous mass obtained is slurried with toluene, allowed to stand, and the solids subsequently filtered oil and dried. Upon recrystallization a white crystalline product possessing a melting point of 177-l78 C. believed to be 4-ch1oroa,a'-bis( 5 -chloro-3 -benzyl-2-hydroxy-phenyl) -2, 6-xyleno1 OH OH OH aHrCH CH CH:- CHzCsll:

Cl 1 Cl is obtained.

By replacing 4-chloro-o-cresol of Example I with an equimolar proportion of 4-bromo-o-cresol and carrying out the condensation with 5-chloro-Z-hydroxy-m-xylenea,a-diol in substantially the same manner a good yield of 4-chloro-a,a-bis 5 -bromo-2-hydroxy-m-tolyl) -2,6-xylenol is obtained. Similarly by the employment of 4-bromo-ocresol and 5-brorno-Z-hydroxy-m-xylene-a,a'-diol as reactants a good yield of 4-bromo-a,a-bis(5-bromo-2-hydroxym-tolyl) -2,6-xylenol is obtained. Similarly by the employment of 2-is-obutyl p chlorophenol and 2-n-heptyl-pbromo-phenol, respectively, as reactants with S-chloro-Z- hydroxy-rn-xylene-a,a-diol good yields respectively of 4-chloro-a,a-bis(3-isobutyl-5-chloro-2-hydrpxy pheny1)- 2,6 xylenol and 4-chloro-a,a'-bis(3-n-heptyl-5-bromo-2- hydroxy-phenyl)-2,6-xylenol are obtained.

The alkali metal salts, particularly the mono-alkali metal salts, of the halogenated tris-phenols of this invention are conveniently prepared by heating in suitable proportions a halogenated tris-phenol with an aqueous solution of an alkali metal hydroxide, such as potassium hydroxide, sodium hydroxide or lithium hydroxide. However, the diand tri-alkali metal salts in many instances require more drastic conditions, as for example refluxing the tris-phenol with a mixture of alcohol and the alkali metal hydroxide in the necessary proportions.

As exemplary of this invention 4-chloro-a,a'-bis(5 chloro-2-hydroxy-m-tolyl)-2,6-xylenol and 4-chloro-a,a'- bis- 5-chloro-2-hydroxy-m-tolyl) -3 -methyl-2,6-xylenol are, respectively, compounded in a detergent composition and compared to a detergent composition containing an isomer of the former halogenated tris-phenol. The tris-phenols listed below are, respectively, incorporated in an Ivory brand white high grade tallow soap to form 2% by weight compositions, that is a ratio of one part of halogenated tris-phenol to 49 parts soap. Aliquots of each are added to a nutrient agar so as to give concentrations of 0.17 p. p. m., 0.34 p. p. m., 0.67 p. p. m., 1.25 p. p. m. and 2.5 p. p. m. of the halogenated tris-phenol in the nutrient agar. The agar in each case is then poured into a petri dis, allowed to harden and then is streaked with a 24 hour old culture of Staphylococcus aureus of standard resistance. The incubation in each case is made at 37 C. for 72 hours and the degree of growth is noted below:

By replacing any one of the aforementioned halogenated iris-phenols of the aforedescribed detergent compositions with an equal weight of either 4-chloro-a,a-bis(5-bromo- 2-hydroxym-tolyl)-2,6-xylenol or 4-bromo-a,a-bis(5- bromo-2-hydroxy-rn-tolyl)-2,6-xylenol and similarly evalmating excellent control of Staphylococcus aureus is obtained. Good control of staphylococci is obtained by the usage of either 4-chloro-a,a-bis(3-benzyl-5-chloro-2-hydroxy-phenyl)-2,6-xylenol, or 4-chloro-a,a-bis(S-chloro- 3'ethyl-2-hydroxy-phenyl)-2,6-xylenol. Good control of staphylococci is obtained also by the usage of the monosodium salt of 4-chloro-a,a'-bis(3-ethyl-5-chloro-2-hydroxy-phenyl)-2,6-xylenol and the mono-potassium salt of 4-bromo-a,a'-bis(3-allyl-5-chloro-2-hydroxy-phenyl)- 2,6-xylenol.

' phenol of this invention or its alkali metal salt or mixtures thereof have proved satisfactory in some instances. However, it is preferred to employ amounts in the order of l-3% by weight. While larger amounts can be employed, as for example up to 10% by weight, the upper limit is determined by practical considerations.

The halogenated tris-phenols of this invention or the alkali metal salts thereof or mixtures thereof may be added to the detergent composition in any suitable manner during the crushing or milling or similar operation. The antiseptic agents of this invention may be first dissolved in a suitable solvent and then incorporated in the detergent if so desired. In general any method which results in the halogenated tris-phenols of this invention or their alkali metal salts thereof or mixtures of said phenols and said salts being uniformly incorporated in the final detergent composition is satisfactory.

While the invention has been described relative to several particular embodiments it is not so limited but that many variations and modifications which are obvious to those skilled in the art to which this invention appertains may be made without departing from the spirit or scope of the invention.

This application is a continuation-in-part of application Serial No. 218,704, filed March 31, 1951.

What is claimed is:

1. As a new compound a member of the group consisting of a halogenated tris-phenol and its alkali metal salts, the said halogenated tris-phenol being of the formula H OH OH R) -CH:-- CH R2 X... X X"..

where R1 and R2 are hydrocarbon radicals containing not more than eight carbon atoms, where R3 and R4 are selected from the group consisting of hydrogen atoms and short chain alkyl radicals, where X, X and X" are halogen atoms having an atomic weight greater than 19.00 but less than 80, and where m and n are whole numbers from 1-3.

2. A halogenated tris-phenol of the formula OH OH OH R CH CHP R2 XII xI/II X! x X! 6 where R1 and R2 are alkyl radicals containing not more than 4 carbon atoms, and where X, X, X, X' and X" are halogen atoms having an atomic weight greater than 19.00 but less than 80.

3. A halogenated tris-phenol of the formula on on on mgcnhgonrom X X x" where R; and R2 are alkyl radicals containing not more than 4 carbon atoms and where X, X and X are halogen atoms having an atomic weight greater than 19.00 but less than 80.

4. A halogenated tris-phenol of the formula (RH OH OH CIhUCHz-OCH-QCH; X X X" where X, X and X" are halogen atoms having an atomic weight greater than 19.00 but less than 80.

5. 4 chloro a,a bis(5 chloro 2 hydroxy mtolyl) -2,6-xylenol.

6. 4 chloro a,a' bis(5 bromo 2 hydroxy mtolyl) -2,6-xylenol.

7. 4 bromo a,a bis(5 bromo 2 hydroxy mtolyl) -2,6-xylenol.

8. 4 chloro a,a' bis(5 chloro 2 hydroxy mtolyl -3-methyl-2,6-xylenol.

9. 4 chloro a,a' bis(5 chloro 3 ethyl 2- hydroxy-phenyl) -2,6-xyleno1.

Marsh et al. (A) Ind. and Eng. Chem., vol. 38, pp. 701-5 (5 pp., July 1946).

Marsh et al.: Ind. and Eng. Chem., vol. 41 (1949), pp. 2176-2184 (9 pages). 

2. A HALOGENATED TRIS-PHENOL OF THE FORMULA 